Thianaphthene 1,1-dioxide compounds



United States Patent 3,099,658 THIANAPHTHENE 1,1-DIOXIDE COMPDUNDS Henry Bluestone, University Heights, Ohio, assignor to Diamond Alkali Company, Cleveland, Ohio, at corporation of Delaware No Drawing. Filed Feb. 11, 1960, Ser. No. 7,982 6 Claims. (Cl. 260-3321) This invention relates to a novel class of biologically active compounds and to methods for preparing and using these compounds.

More specifically, the compounds of the present invention are pesticides having the generic formula Exemplary of compounds falling within the above generic formula are the following:

Oz 3,3a-dichlore-3a,4,7,7a-tetrahydrothianaphthene 1,1-dioxide 3,3a-dichloro-3a,4,7,7a-tetrahydro-6-methylthianaphthene 1,1-dioxid C1 01 Ol- -01 C1 C1 (cis) (trans) O1 S n 01 S u 09 02 (III) (IV) cis and trans-3,3a,5,6-tetrachloro-3a,4,5,6,7,7a-hexahydrothianaphthene 1,1-dioxides Wi-thIregard to the material indicated as (II) above, it is not known for certain whether this has the structure shown or whether the methyl group is substituted in the five position, i.e.,

mo k 01 bll 3,3a-dichloro-3a,4,7,7a-tetrahydrO-S-methylthianaphthene 1,1-dioxide the material is a mixture of both tne In all probability,

From a consideration of 5- and o-methyl compounds.

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the preparation reaction mechanism and the polarization of the reactants, it is believed that formation of the 6- methyl compound is favored. However, when reference is made hereinafter to the 6-methyl compound, it is to be understood that this is intended to include also the S-methyl compound and mixtures of the 5- and 6 methyl compounds.

It is to be further noted that the compounds indicated hereinabove as (111) and (IV) are cisand trans-isomers, having different melting points, although it is not known for certain which isomer is cis and which is trans. Additionally, as will be shown more fully hereinafter, the isomeric compounds also exhibit a different degree of biological activity and, more specifically, pesticidal activity. In view of this, the cisand trans-isomeric forms of this compound will hereinafter be treated as separate compounds.

It is to be understood, that as used hereinafter, the term pesticide or pesticidal composition is meant to refer \to those toxicant compositions which are effective in killing or controlling the growth of plants, insects, nematodes, microorganisms, fungi, bacteria and the like, and is intended to refer broadly to those compositions commonly known as insecticides, bactericides, fungicides, nematocides, herbicides, and the like.

Additionally, the term halogen, as used hereinafter, is intended to refer broadly to fluorine, chlorine, bromine, and iodine. However, because of its low cost and ready availability, the preferred halogen in the compositions of the present invention is chlorine, and for this reason, primary reference hereinafter will be made thereto.

While compounds of this invention may be employed in a variety of applications, biologically active or otherwise, it will be understood, of course, that such compounds may be utilized in diverse formulations, both liquid and solid, including finely-divided powders and granular materials, as well as liquids, such as solutions, concentrates, emulsifiable concentrates, slurries and the like, depending upon the application intended and the formulation media desired.

These compounds may be used alone or in combination with other known biologically active materials so as to provide a formulation which will be effective in controlling a variety of pests.

Thus, it will be appreciated that compounds of this invention may be employed to form biologically active substances containing such compounds as essential active ingredients thereof, which compositions may also include finely-divided dry or liquid diluents, extenders, fillers, conditioners, including various clays, diatomaceous earth, talc, spent catalyst, alumina-silica materials, liquids, solvents,

diluents or the like, including water and various organic liquids, such as benzene, toluene, chlorinated benzene, acetone, cyclohexanone, Xylene, carbon d-isulfide and various mixtures thereof.

When liquid formulations are employed, or dry materials prepared which are to be used in liquid form, it may be desirable in certain instances additionally to employ a wetting, emulsifying or dispersing agent to facilitate the use of the formulations, e.g., Triton X-l55 (alkyl aryl polyether alcohol, U.S. Patent No. 2,504,064).

Additionally, it is to be understood that the term carrier"as employed in the specification and claims hereof is intended to refer broadly to materials constituting a major proportion of a biologically active or other formulation, and hence includes finely-divided materials, both liquids and solids, as aforementioned, conveniently used in such applications.

In genenal, compounds of thevpresent invention may be prepared by combining a conjugated diene and a particular dienophile and causing them to react in a Diels- Alder reaction. The resulting product is then collected as and a compound having the generic formula R HC=C-C=CHR4 are combined in a Diels-Alder reaction so as to form a product having the generic formula wherein the R groups are selected from the group consisting of hydrogen and alkyl and X is halogen. This productis then separated as a compound within the generic structure of the present invention or it maybe further reacted as by halogenation to form other compounds falling within the generic formula 'of the present invention. The Diels-Alder reaction may be carried out in any suitable solvent, such as for example, methanol, and similarly, the halogenation of the Diels-Alder reaction product may also [be carried out in a suitable solvent, such as chloroform. Moreover, theproduct ofeither the Diels- Alder reaction or of the halogenation reaction may he purified in any 'suitable'manner, asfor'example, by 'distillation or by recrystallization from any suitable solvent, such as methanol.

Inorder that those skilled 'inthe art'can better under- "stand the method of thepresent invention,-and themanher in which it'may be practiced, the following specific examplesare given. Inthese'examples, the 3,4-dichlorothiophene l,1-1dioxide is prepared according to the 'procedure set forth in U.S. application Ser. No. 709,449, now U.S. Patent 2,976,297. Moreover, the 3,3;4,4-tetrachlorotetrahydrothiophene -1,1-dioxide referred to in 'this'preparation is prepared according to the method set forth in U.S. application Ser. No. 645,676, "now U.S. .Patent EXAMPLE 1 Preparation of 3,3a-Dichl0r0-3a,4,7,.7a Tetrahydrothianaphthene 1,1-Di0xide (1) Calculated, Actual, Element percent by percent'by weight weight 0 '40. 2 40. l H 5 2 36 CI 2 EXAMPLE 2 A tomato foliage disease test is conducted measuring the ability of the product of Example 1 toprotect tomato foliage against infection by the early blight fungus Alternaria solani. Tomato plants 5 to 7 inches high of the variety Bonny Best are employed. The plants are sprayed with ml. of test formulation at 2000 ppm. and 400 ppm. test chemical in combination with 5% acetone-- 0.01% Triton Xl55-and the balance Water at 40 lbs. air pressure while being rotated on a turntable in a spray chamber. After the spray deposit is dry, the treated plants and comparable untreated controls are again sprayed as described above, with a sporangial suspension containing approximately 20,000 conida of A. solani per ml. The plants are held in a 100% humid atmosphere for 24 hours at 70 F. to permit spore germination and infection. One day after removal from the humid atmosphere lesion counts are made on the three uppermost fully expanded leaves. Data based on the number of lesions obtained on the control plants shows 99% disease control at 2000 ppm. and 88% disease control at 400 ppm.

EXAMPLE 3 Fungicidal utility is further demonstrated by the ability of the product of Example 1 to protect tomato plants against the late blight fungus, Phytophthora infestans. The method employs tomato plants 5 to 7 inches high of the variety Bonny Best. 100 ml. of the test formulation (2000 ppm. and 400 p.p.m. of the test compound of Example 1, 5% acetone-0.01% Triton Xl55-the balance water) are sprayed on the plants at 40 lbs. air pressure while the plants are being rotated on a turntable in a spray chamber. After the spray deposit is dry, the treated plants and comparable untreated controls are again sprayed as described above, with a sporangial suspension containing approximately 150,000 sporangia of P. infestans per ml. 30 seconds at 20 lbs. The plants are held in a 100% humid atmosphere for-24 hours at 60 F. to permit spore germination and infection. After 2 to 4 days, lesion counts are made on the three uppermost fully expanded leaves. Comparing the number of lesions on the test plants and control plants shows disease control of 94% and 68%, respectively, on the test plants.

EXAMPLE 4 In showing nematocidal activity of the product of Example 1, composted greenhouse soil in one-half gallon glazed'crocks-is infestedwith 3-5 g. of knotted or galled tomato roots containing root knot nematodes, Melo dogyne species. Treatment at a rate equivalent to 256 lbs/acre (385 mg./crock) is effected by mixing the test chemical intimately with the soil. An indicator crop of three tomatoes are transplanted into treated crooks and into infested and non-infested check crooks 4 to 7 days aftertreatment. The'degree of infection which is measured by the number and size of galls formed compared to checks is used as an index of the nematocidal activity of the tes-t'material. Using the product of Example 1, results show no root knot infection.

EXAMPLE 5 The following test measures the ability of the product of Example 1 to protect pea seeds and seedlings from seed decay and damping oif fungi (Pythium and Fusarium species). In this test, infested soil in 4 x 4 x 3 inch plant band box is treated by a soil drench-mix method at the equivalent rate of 32 lbs./ acre. Treatment is accomplished by pouring 70 ml. of a 2000 ppm. test formulation (2000 ppm. of the product of Example 1, 5% acetone-0.01% Triton Xbalance water) on the surface of the soil. This is allowed to stand until the next day when the soil is removed from each box and thoroughly mixed before being replaced in the box. Three days after treatment, 25 pea seeds, variety Perfection, are planted to a uniform depth per box. Untreated checks are included in each test in addition to a check planted in sterilized soil. Percentage stand recorded 14 days after planting shows 83% disease control.

5 EXAMPLE 6 The large seed leaves of 10-day old pinto bean plants, 4 plants per inch pot are used in this test. The product of Example 1 is applied to the soil in a test formulation (0.2% of the product of Example 1, 5% acetone, 0.01% Triton X-l55, and the balance water). The concentrations of test chemical used are equivalent to 64 and 32 lbs./ acre. Immediately following application of the test chemical to the soil surrounding the plants, the plants are sprayed with a spore suspension of the rust fungus, Uromyces phaseoli. This spore suspension is prepared by taking 30 mg. of freshly harvested spores and mixing with 48 mg. of talc. This is then diluted with water at the rate of about 1 mg. of the talc-spore mixture to 1.7 ml. of distilled water.

After spraying the spores on the seed leaves of the bean plants, they are placed in a water saturated atmosphere for 24 hours at 60 F. After incubation the plants are removed to controlled lgneenhouse conditions and 910 days after exposure rust lesions are counted. The date observed is converted to percentage disease control based on the number of lesions obtained on untreated control plants. Using this procedure, results indicate 95 and 85% disease control, respectively, for the two concentrations used.

EXAMPLE 7 Preparation of 3,3a-Dichlr0-3a,4,7,7a-Tetrahydro-S and/ or 6-Methylthianaphthene 1,1-Dioxide (II) and/0r (V) A solution of 111.0 g. (0.6 mole) 3,4-dichlorothiophene-1,1-'dioxide in 1360 ml. methanol is stirred at 45 to 55 C. while 68.0 g. (1.0 mole) of isoprene is added slowly. Stirring is continued for an hour, then a second mole of isoprene is added and stirring at 50 C. is continued for three more hours. The solution is left overnight at room temperature and then distilled. The 48.2 g. of crude liquid which distills above 90 C. at 0.8 mm. is redistilled, yielding 29.5 g. (19%) of pale yellow (II) and/or (V) between 133 and 136 C. at 0.6 mm. This has a refractive index (N of 1.5550 and a density (D of 1.4215.

Calculated, percent by weight Actual, percent by weight Element 43. 2 3. 87 Present 3. 98 Present EXAMPLE 8 Tomato plants, variety Bonny Best, growing in 4" pots are treated by pouring a test formulation (2000 p.p.m. of the product of Example 7, 5% acetone0.01% Triton X155-balance water) into the pots at an equivalent rate of 128 lbs./ acre (102 mg./pot). The tomato plants are 3 to 4" tall with the rtrifoliate leaves just starting to unfold at time of treatment. The plants are exposed to powdery mildew continuously after seedling emergence so that at the time of treatment infection has occurred. After to 14 days, observation indicates 97% disease control by comparison to untreated control plants.

EXAMPLE 9 In order to make an in vit-ro evaluation of the product of Example 7 as a contact ncrnatocide, nematodes (Panagrellus redivivus), are exposed to the test chemical in small watch glasses (27 mm. diameter x 8 mm. deep), within a 9 cm. Petri dish. An aqueous test formulation (1000 p.p.m. of the product of Example 7-5% acetone-0.01% Triton X-1 55 balance water) is used. Results are recorded 24 hours afiter treatment and from these it is shown that 100% mortality is observed.

EXAMPLE 10 The product of Example 7 is tested using the fungicide evaluation procedure of Example 6. The concentration of the test chemical used is equivalent to 64 lbs./ acre and the results obtained show 93% disease control.

EXAMPLE 11 Preparation of Cisand Trans-3,3a,5,6 Tetrachloro- 3a,4,5,6,7,7a H exahydrothianaphethene 1,1 Dioxides (Ill) and (IV) A solution of 30.0 g. (0.125 mole), 3,3-dichloro- 3a,4,7,7a-tetrahydrothianaphthene 1,1 dioxide (the prodnot of Example I) in ml. of chloroform is stirred while 13.2 g. (0.186 mole) chlorine is added during nineteen minutes at a maximum temperature of 58 C. The solvent is removed under reduced pressure, leaving 39.1 g. of a colorless viscous liquid. Trituralting with methanol induces crystallization of 1.5 g. white solid. Repeated fractional crystallization of this solid from methanol produces both tetragonal plates, M.P. to 141 C. and needle-shaped crystals M.P. 180.5 to 182.5 C. Chlorine determinations shows these to be cisand trans-isomers of the desired tetrachlor-o compound. The lower melting product (III) is believed to have a cis arrangement of the chlorine atoms at the 5 and 6 positions and the higher melting isomer (IV) is believed to have the trans configuration.

Compound: Found III M.P. 140-141 0., Cl, 45.7%. IV M.P. 180.5-182.5 (3., Cl, 45.4%. Calculated Cl, 45.7%.

EXAMPLE 12 Product III of Example 11 is tested using the fungicide evaluation procedure of Example 2. The concentrations used and the results obtained are as follows.

Concentration, p.p.m.: Percent disease control Product III of Example 11 is tested using the fungicide evaluation procedure of Example 3. The concentrations used and the results obtained are as follows.

Concentration, p.p.m.: Percent disease control EXAMPLE 14 Product III of Example 11 is tested using the funfiicide evaluation procedure of Example 6. The concentration used is equivalent to 64 lbs./ acre and the results show 69%disease control.

EXAMPLE 15 Using the large seed leaves of 10-day old pinto bean plants, 'a test formulation made up of (0.2% of product III of Example 11, 5% acetone-0.01% Triton X- balance water) is sprayed on the foliage of the plants, and allowed to dry. Thereafter, the plants are exposed to uredospores of the bean rust fungus, Uromyces phaseoli. Thus exposed seed leaves of bean plants are then placed in a saturated atmosphere for 24 hours at 60 F. After incubation the plants are removed to con trolled greenhouse conditions and 9 to 10 days after exposure, rust lesions are counted. The data observed is converted to percentage disease control based on the number of lesions obtained on the control plants. The concentration of product 111 of Example 11 is 512 p.p.m. and the results obtained show 82% met con-trol.

EXAMPLE 16 Product IV of Example 11 is tested using the fungicide evaluation procedure of Example 2. The concen trations used and the results obtained are as follows.

Concentration, p.p.-rn. Percent disease control 512 83 256 74 128 70 64 62 effective.

While there have been described various embodiments of the invention, the methods and products described are not intended to be understood as limiting the scope of the invention, as it is realized that changes therein are possible and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention in Whatever form its principle may be utilized.

What is claimed is:

I1. The compound having the formula I OH wherein Y is a bivalent radical selected from the group consisting of R R R R R and R are selected from the group consisting of hydrogen 'and methyl and X is halogen.

2. 3,3a dichloro 3a,4,7,7a -tetrahydrothianaphthene 1,1-dioxide.

3. 3,3a-dichloro 3a,4,7,7a tetrahydro 6 methylthi-an-aphthene 1,1-dioxide.

4. Cis 3,3a,5,6 tetrachloro 3a,4,5,6,7,7a heXa hydrothianaphthene 1,1-dioxide.

5. Trans 3,3a,5,6 tetrachloro 3a,4,5,6,7,7a hexahydrothianaphthene 1,1-dioxide.

6. 3,3adichloro 3a,4,7,7a tetrahydro 5 methylthianaphthene 1,1-dioxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,644,426 Elmer Dec. 29, 1953 2,632,545 Mahan et al June 29, 1954 2,758,955 Johnson et a1 Aug. 14, 1956 2,781,289 Elmer et a1. Feb. 12, 1957 2,882,278 McConnell et al. Apr. 14, 1959 2,928,766 Rosen Mar. 15, 1960 OTHER REFERENCES Noller: Texbook of Organic Chemistry, 2nd edition, 1958, pp. 50-52.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,099,658 July. 30, 1963 Henry Bluestone It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as correc ted below Column 6, line 16, for 1.5" read 21.5 line 55, for "funfiicide" read fungicide same column,

Signed and sealed this 21st day of January 1964.

(SEAL) Attest: EDWIN REYNOLDS ERNEST W. SWIDER Attesting Officer Ac ting Commissioner of Patents 

1. THE COMPOUND HAVING THE FORMULA 